Light-sensitive silver halide color photographic material having improved graininess upon color development

ABSTRACT

WHEREIN R4 IS HYDROGEN, LOWER ALKYL OR ARALKYL AND X AND X&#39;&#39; ARE INDIVIDUALLY HYDROGEN, ALKYL, ALKOXY OR HALOGEN. UPON DEVELOPMENT A COLOR IMAGE HAVING EXCELLENT GRAININESS IS OBTAINED.   1-R4,3-((4-X-PHENYL)-SO2-),4-(4-X&#39;&#39;-PHENYL)-PYRAZOLE   WHEREIN R1, R2 AND R3 ARE INDIVIDUALLY HYDROGEN, LOWER ALKYL, ALKENYL, ARYL OR ALKYL, AND A PYRAZOLE TYPE COMPOUND OF THE FORMULA   1-R3,5-((1-R2-TETRAZOL-5-YL)-S-S-)-1H-TETRAZOLE   1-R1,5-(HS-)-1H-TETRAZOLE OR   A COLOR PHOTOGRAPHIC MATERIAL CONTAINS A SILVER HALIDE LIGHT-SENSITIVE, COUPLER-CONTAINING EMULSION LAYER, A MERCAPTOTERTRAZOLE TYPE COMPOUND OF THE FORMULA

United States Patent US. Cl. 96-100 4 Claims ABSTRACT OF THE DISCLGSURE A color photographic material contains a silver halide light-sensitive, coupler-containing emulsion layer, a mercaptotetrazole type compound of the formula I I] I ll ll N N\ /N //N N N N wherein R R and R are individually hydrogen, lower alkyl, alkenyl, aryl or aralkyl, and a pyrazole type compound of the formula N l Q wherein R is hydrogen, lower alkyl or aralkyl and X and X are individually hydrogen, alkyl, alkoxy or halogen. Upon development a color image having excellent graininess is obtained.

This invention relates to a light-sensitive color photographic material which has been improved in graininess of dye image obtained by color development.

For improvement in graininess of dye image, there have heretofore been known a process in which the amount of silver halide is increased, and a process in which a specific chemical is added to lower coupling rate. However, the former process has such drawback that a large amount of expensive silver halide is required to make the production cost high, and the latter has such drawback that it is applicable only to the limited species of couplers or brings about desensitization.

With an aim to overcome the above-mentioned drawbacks, we made extensive studies to find a novel process in which a color image having a markedly excellent graininess can be obtained by using a mercaptotetrazole type compound of the general Formula I shown below in combination with a pyrazole type compound of the general Formula II shown below.

That is, the present invention provides a light-sensitive color photographic material excellent in graininess of dye image by adding to a light-sensitive silver halide emulsion, which has or has not been spectrally sensitized, a mercaptotetrazole type compound of the general Formula I,

N N N (I) wherein R R and R are individually a hydrogen atom, or a lower alkyl (C to C group, an unsaturated chain 3,717,465 Patented Feb. 20, 1973 hydrocarbon residue, an aryl group or an aralkyl group, in combination with a pyrazole type compound of the general Formula II,

Exemplified compound No.

I l C H: 01

l C I W N N Exempllfided co un NE R:

[II-16 H [11-17 -Cz c -C2 s Q Q Q I Br Br OCH! OC l Br (11-24 CisHss -C1s as Examples of the compounds of the general Formula II Exemplified compound No.

Both the compound of the general Formula I and the compound of the general Formula II may individually be used in the form of a mixture of two or more so as to be in conformity to the desired purpose. Further, the compound of the Formula I and the compound of the Formula II may be incorporated into one layer or may separately be incorporated not only into adjacent layers but also into auxiliary layers such as sub layer, inter layer, protective layer, etc. The compounds may be added to a silver halide photographic emulsion at any stage of preparation thereof, but it is more effective to add them during second ripening or prior to coating. In case the compounds are desired to be added during second ripening, temperature, time or the like conditions for second ripening may be suitably controlled so as to attain the most excellent photographic properties.

The amounts of the compounds to be added are not particularly limited, and the optimum amounts vary depending on the kind of the compound. Preferably, however, the amount of the compound of the Formula I is to 10- mole per mole of AgX, and the amount of the compound of the Formula II is 10" to 1 mole per mole of AgX. Among the compounds of the Formulas I and H, those which are lipophilic may be used in the form of dispensions in a high boiling organic solvent, e.g. dibutyl phthalate, or in a low boiling organic solvent, e.g. chloroform, acetone or dimethylformamide, while those which are water-soluble may be used in the form of dispersions in a water-miscible organic solvent or in an aqueous alkali solution.

The photographic emulsion used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide and silver iodobromide. Further, the emulsion may have been subjected to spectral sensitization by use of any of cyanine dyes and merocyanine type compounds, or may have been subjected to chemical sensitization by use of any of sulfur-containing compounds, noble metal salts, polyalkylene oxide derivatives and reducing compounds.

As a hardener, there may be used Formalin for example, and as a coating aid, there may be used a synthetic surface active agent or a natural surface active compound, e.g. saponin. Usable couplers are those which develop colors by means of p-phenylenediamine type color developers and include, for example, yellow couplers having benzoylacetanilide groups, magenta couplers having pyrazolone nuclei, indazolone nuclei or cyanoacetyl groups, and cyan couplers having phenol or naphthol nuclei. These couplers may have in the active methylene or methine position a substituent capable of releasing by coupling reaction, e.g. a halogen atom or an arylazo, aryloxy or arylthio group, and may further contain in the molecule either one or both of a group capable of providing diffusion resistance, e.g. a long chain alkyl group or an alkylphenoxy group, and a group capable of providing water solubility, e.g. a sulfonic group or a carboxyl group. Among these couplers, those which are lipophilic may be used in the form of dispersions in a high boiling organic solvent, e.g. dibutyl phthalate, or in a low boiling organic solvent, e.g. chloroform, acetone or dimethylformamide, While those which are watersoluble may be used in the form of solutions in alkali or the like, and added directly to a silver halide emulsion or incorporated into a color developer solution.

The light-sensitive layer may be composed of protective layer, blue-sensitive layer containing a yellow coupler,

sample was scanned by use of a microdensitometer having an open aperture of 25p.)

TABLE 1 Amount of Amount of compound (I) (g. per compound (II) (g. Relative mole of AgX) per mole of AgX) speed Fog RMS 100 0. 14 85 96 0. 10 83 90 0.08 80 103 0. 08 83 100 0. 08 83 99 0. 08 61 89 0. 06 58 101 0. 08 65 98 O. 08 70 102 0.06 62 0.06 93 0.07 64 0.06 104 0. 08 58 4, 0.06 100 0. 06 60 [I 4, 0.06 g 100 0.08 63 [I 4, 0.06 g [III-10, 1.4 g... 98 0.06 58 [114, 0.06 g [III-12, 1.4 g 96 0. 06 54 As seen in Table 1, the photographic films prepared by use of the compound (I) in combination with the compound (II) are greatly decreased in RMS graininess without any substantial desensitization, and hence are obviously improved in granularity of dye image.

EXAMPLE 2 A high speed, light-sensitive silver iodobromide photographic emulsion (containing 4.5 mole percent of AgI, and 160 g. of gelatin per mole of AgX) was subjected to second ripening, and then incorporated with 1.4 g./mole AgX of S-methyl 7 hydroxy 1,3,4 triazaindolizine and 0.2 g./mole AgX of a spectral sensitizing dye of the structure shown below to prepare a green-sensitive emul- I I SON 02H. C2H5 Subsequently, the emulsion was incorporated with each of the compounds (II)-1 and (II)-7 in such amount as shown in Table 2.

On the other hand, each of the couplers (3) and (4) of the structures shown below was dispersed by means of a high speed rotary mixer together with such components as set forth below to form coupler dispersions (1) and (2) of the compositions shown below in which the amount of each component is per mole of AgX.

Coupler (3): I

(t) emu-Q cm 0 ONE-Q Coupler (4):

Subsequently, the emulsion was mixed with each of the coupler dispersions, charged with 120 ml. of 1% Formalin and 300 ml. of 5% saponin per mole of AgX, and coated on a cellulose triacetate film base to a dry film thickness of 5 followed by drying, to prepare samples. These samples were subjected to the same development as in Example 1 to obtain the results set forth in Table 2.

TABLE 2 Amount of compound (II) Coupler Relative (g. per mole of AgX) dispersion speed Fog RMS 1 100 0. 11 73 (ID-1, 1.5 g 2 100 0. 08 49 (H)-7, 1.5 g 2 98 0. 06 46 In Table 2, marked improvement in graininess can be observed also in the case of the oil-soluble compound (I), when it is dispersed together with a coupler and used in combination with the compound (II).

EXAMPLE 3 A high speed, light-sensitive silver iodobromide photographic emulsion (containing 2.0 mole percent of AgI, and 180 g. of gelatin per mole of AgX) was subjected to second ripening, and incorporated with 1.4 g./mole AgX of S-methyl 7 hydroxy 1,3,4 triazaindolizine and then with compounds (I) and (II) in such a combination as shown in Table 3. Subsequently, the emulsion was mixed with g. per mole of AgX of a coupler of the structure shown below in the form of a solution in aqueous caustic soda and Water.

Coupler (5):

01511310 ONE-QC 0cm 0 ONE- Thereafter, the emulsion was charged with 100 ml. of

COOH

OOH

yellow filter layer, green-sensitive layer containing a magenta coupler, inter layer, red-sensitive layer containing a cyan coupler, antihalation layer and support in this order from the upper-most layer, though the order varies depending on application of the resulting photographic material, and the order of green-, redand blue-sensitive layers, may also be successfully adopted. If desired, the layers may be composed of one or two layers.

The support used in the present invention is ordinarily a paper or a natural or synthetic high polymer film of the cellulose acetate or polyester type.

Development of the thus obtained light-sensitive color photographic material of the present invention may be carried out according to any of such procedure that a dye image is directly formed by the first development, like in the case of a color negative, or such procedure that development is first effected by use of a black-and-white developer such as Metol or hydroquinone, and then a dye image is formed, like in the case of reversal color development.

Typical examples of the color developer used for the photographic material according to the present invention are sulfates, hydrochlorides or sulfites of N,N-diethyl-p-phenylenediamine, N-ethyl-N hydroxyethyl-pphenylenediamine, N-ethyl-N-hydroxyethyl Z-methyl-pphenylenediamine, N-ethyl-N-B methanesulfonamidoethyl-3-methyl-4-aminoaniline, etc.

The present invention is illustrated in further detail below with reference to examples, but the modes of practice of the present invention are not limited only to these examples, and various modifications are possible within the scope of the invention.

EXAMPLE 1 A high speed, light-sensitive silver iodobromide photographic emulsion (containing 4.0 mole percent of AgI, and 180 g. of gelatin per mole of AgX) was subjected to second ripening and then incorporated with 0.2 g./ mole AgX of a spectral sensitizing dye having the struc ture shown below to prepare a red-sensitive emulsion.

Spectral sensitizing dye:

CzHs

Cl CzHi Coupler 1 CONH(CH2)40 5 11) 6 Coupler (2) o oNH oH, ,-oiHn( 0 (2511110) II N Q-ooom Composition of coupler dispersion:

Coupler (1) g.... 10 Coupler (2) g 4 2,5-di-(t) octylhydroquinone g 0.5 Tricresyl phosphate g 20 Ethyl acetate g 30 5% Alkanol B (trademark of Du Pont) "ml-.. 15 3% Gelatin ml 400 The emulsion was mixed with the thus prepared coupler dispersion, charged with ml. of 1% Formalin and 300 ml. of 5% saponinper mole of AgX, and coated on a cellulose triacetate film base to a dry film thickness of 3.5;, followed by drying, to prepare a photographic film. Thereafter, the photographic film was exposed through an optical wedge and then treated in the following Way.

(1) Color development: 20 C. 12 min.

Composition of developing solution:

Water to make 1,000 m1.

(3) First fixing: 20 C. 5 minutes.

Composition of fixing solution:

Sodium thiosulfate g 150 Water to make 1,000 ml.

(4) Water-washing: 5 minutes. (5) Bleaching: 20 C. 6 minutes.

Composition of bleaching solution:

Potassium ferrocyanate g- 100.0 Potassium bromide g 50.0 Water to make 1,000 m1.

(6) Water-washing: 5 minutes.

(7) Second fixing: The composition of fixing solution was the same as in the first fixing.

(8) Water-washing: 10 minutes.

(9) Drying.

The relative speed, fog and RMS graininess at the point of a color density of 0.3 of the photographic film after the color development were as set forth in Table 1. (The RMS graininess referred to herein is a value of 1,000 times the standard deviation of density value measured when a uniformly exposed and developed 9 Formalin and 300 ml. of saponin per mole of AgX, and coated on a triacetate film base to a dry film thickness of 5p, followed by drying, to prepare a photographic film. The photographic film was exposed through an optical wedge to a light of regulated amount, developed at 20 C. for minutes by use of a color developer solution of the composition shown below, and then subjected to the same fixing and the like treatments as in Example 1.

Composition of color developing solution: G. Anhydrous sodium sulfite 2.0 4-amino-N,N-diethylaniline hydrochloride 5.0

Sodium carbonate (monohydrate) 50.0

From Table 3, it is understood that marked improvement in graininess can be attained also in the case of a combination of two kinds of the compound (I) and one kind of the compound (II) or a combination of one kind of the compound (I) and two kinds of the compound (II).

EXAMPLE 4 A high speed, light-sensitive silver iodobromide photographic emulsion (containing 4.5 mole percent of AgI, and 160 g. of gelatin per mole of AgX) was subjected to second ripening, and then incorporated with 1.4 g./mole AgX of 5-methyl-7-hydroxyl-1,3,4-triazaindolizine and each of the two solutions (1) and (2) of the compositions 10 Composition of coupler dispersion:

Coupler (6) g 82 2,5-di-(6)-octylhydroquinone g.. 3 Tricresyl phosphate g 60 Ethyl acetate g 250 5% alkanol B ml 320 3% gelatin ml 2,000

Subsequently, each of the above-mentioned emulsions was mixed with the thus prepared coupler dispersion, charged with 120 ml. of 1% Formalin and 500 ml. of 5% saponin per mole of AgX, and coated on a triacetate film base to a dry film thickness of 5 followed by drying to prepare samples. These samples were subjected to the same treatments as in Example 1 to obtain the results as shown in Table 4.

TABLE 4 Relative speed Fog RMS Solution:

As seen in Table 4, the sample according to the present invention is markedly improved in graininess without any loss in speed.

What we claim is:

1. A color photographic material containing a silver halide light-sensitive coupler-containing emulsion layer, at least one compound of the formula shown below to prepare two green-sensitive emulsions. wherein R R and R are individually hydrogen, lower 1, grams Solution 2, grams I l S CN'CzHa C2 5 Compound (1)-5 Compound (ID-4 Methyl alcohol ONO v 1 300 milliliters.

On the other hand, a coupler of the structure shown below was dispersed by means of a high speed rotary mixer together with such components as set forth below to form a coupler dispersion of the composition shown below, in which the amount of each component is per mole of AgX.

Coupler (6):

omm-Qoomconn-Q (U s u (SONH-iJ-CH,

alkyl, alkenyl, aryl or aralkyl, and at least one compound of the formula wherein R is hydrogen, lower alkyl, or aralkyl, and X and X' are individally hydrogen, alkyl, alkoxy or halogen.

wherein the compound of the Formula I and the compound of the Formula H are incorporated into the same layer of said material.

4. The photographic material according to claim 1, wherein the alkenyl group is CH CH=CH References Cited UNITED STATES PATENTS 3,295,976 1/ 1967 Abbott et a1. 96-109 3,311,474 3/1967 Willems et a1. 96109 3,554,756 1/1971 Terashima et a1. 96-100 J. TRAVIS BROWN, Primary Examiner US Cl. X.R. 

